用马赛克形貌装饰法研究碗形分子柱状向列相的向错和分子指向矢分布

选用香兰素为原料,采用传统的三聚成环法,合成了两种碗形CTV系衍生物——CTV-1和CTV-2,前者的外围基团是—OCH3和—OCH2CH3,后者的外围基团是—OCH3和—OCH2COOCH3.两种碗形CTV分子均是热致液晶,呈现向列相典型的粒状织构和单微区的均匀织构,还观察到规则美观的马赛克形貌,每块矩形马赛克的尺寸为数十微米数量级,多次升降温循环能重复出现和消失.发现马赛克形貌实质上是在冻结的向列相织构上结晶化并收缩龟裂而装饰出来的光学图案.通过扫描电镜的研究,观察到马赛克形貌是由片晶组装而成的,每块马赛克就是一块矩形的多层片晶,多层片晶由单层片晶堆积而成.直接观察到片晶的组成单元是直径约1微米的微纤,而微纤应当是束状的碗形分子柱.马赛克形貌装饰在碗形分子柱状向列相上,通过这种新方法观察到s=＋1（δ=0和δ=90°）和s=±1/2多种点向错和Nèel微区壁等周围的分子指向矢分布情况.说明碗形分子柱状向列相与一般向列相有类似的液晶行为,但取向的基本结构单元是碗形分子柱,或者由碗形分子柱组成的束（即微纤）,而不是碗形分子本身.碗形分子柱起了一般向列相中棒状分子的作用,所以本文以一个新名称＂碗形分子柱状向列相＂BCN（Bowlic Columnar Nematic）来表示这种不同常规的向列相.     

含碗形CTV侧基的甲基丙烯酸酯类单体和聚合物

采用三聚法合成外围基团中含羟十一碳氧基的CTV衍生物(CTV-H),然后结合柱层析分离技术合成和分离出外围基团中含单甲基丙烯酸酯基团的CTV衍生物(CTV-M).以CTV-M为单体,本体聚合得到含碗形CTV侧基的甲基丙烯酸酯类聚合物(BPM).CTV-H和CTV-M都具有热致液晶性,是新的碗状液晶.SAXS和WAXD测定表明,液晶结构为六方柱相(Φh),柱直径为4.4 nm和4.8 nm,与理论计算结果相符.而BPM没有液晶性,呈非晶态.     

热致液晶含氯侧基聚芳醚酮的单晶状条带织构

通常主链液晶高分子在受到剪切作用时 ,分子微纤呈周期性锯齿状排列 ,其光学效应表现为在偏光显微镜下可观察到相互平行且与剪切方向垂直的条带织构 [1] .而厚度适中的主链液晶聚合物薄膜经过热处理 ,即使没有受到剪切取向的作用 ,介晶微区的尺寸发展到一定大小时也会形成条带织构 ,即所谓结晶诱导[2 ] 和固化诱导 [3,4 ] 的条带织构 .在所报道的条带织构中 (包括剪切和非剪切 ) ,分子链均平行于膜平面 .本文研究发现 ,热致液晶氯代聚芳醚酮的薄膜样品在其高有序液晶温区经热处理 ,可形成结晶诱导的单晶状条带织构 ,其分子链垂直于膜平面 .…     

用条带织构装饰技术研究液晶全芳共聚酯的取向和非取向膜

用退火使条带织构装饰在全芳共聚酯的取向膜上，在偏光显微镜下同时观察到微纤和条带。微纤分三个层次，即直径分别为数十微米的微纤束、数微米的微纤和０．３微米的亚微纤，退火后三个层次的微纤松弛成不同的形态，微纤束仍笔直沿剪切方向取向，微纤松弛成螺旋形，而亚微纤松弛成波浪形从而观察到条带织构：微纤直径越小越易松弛，另一方面，非取向态织构退火后由亚微纤形成的条带装饰结果直观地揭示了微区内外分子指向矢的分布和它们在边界上的变化。退火时条带织构的形成被解释为分子的弹性回缩力缓慢发生作用使分子松弛所致。     

含柔性间隔基的热致液晶性共聚酯的结晶形态

采用偏光显微镜、扫描和透射电镜从不同层次的结构水平上研究了含柔性间隔基热致液晶性共聚酯的结晶形态。在偏光显微镜下观察到典型的负光性球晶形态,透射电镜揭示了球晶是由厚度为10nm并沿着径向生长的片晶结构所组成,分子链沿晶片厚度方向取向排列。并研究了分子链的刚性程度对热致聚芳酯结晶性质的影响。结果表明,分子链刚性越大其结晶性和球晶的完善性越高。     

席夫碱型液晶冠醚的合成与性质

以4-(4'-烷氧基联苯基-4-羧基)苯甲醛和二氨基二苯并-14-冠-4为原料,通过溶液缩合反应,合成了一系列席夫碱型液晶冠醚.并用元素分析、旋光仪、核磁共振、红外光谱、快原子轰击质谱、基质辅助激光解析电离飞行时间质谱、示差扫描量热法和偏光显微镜对其进行了表征.发现化合物2,4,8I和8Ⅱ加热至各自的熔点以上都能形成液晶态,在液晶态可以观察到手性近晶C相、近晶相、胆甾相和向列相的典型织构.随分子末端烷氧基碳原子数增加,化合物(除2A和4A外)的熔点(Tm)和液晶态的清亮点(Ti)呈规律性变化,近晶相范围渐增,而近晶相-向列相转变温度和向列相温度范围递减.     

液晶性芳香醛化合物的合成

以对羟基苯甲醛和对烷氧基联苯酰氯为原料,采用爱因宏反应,合成了一系列4-(4'-烷氧基联苯基-4-羧基)苯甲醛.化合物的结构通过元素分析、红外光谱、核磁共振和质谱等方法确证.化合物的液晶行为用示差扫描量热法、偏光显微镜和旋光仪等方法表征.结果表明,所有的化合物加热至各自的熔点以上都能形成液晶态.在液晶态可以观察到手性近晶C相、近晶相、胆甾相和向列相的典型织构.含手性中心的化合物都有较高的旋光性,而且在合成反应中旋光性得到保持.随着分子末端烷氧基碳原子数增加,化合物(除2a和4a外)的熔点(T_m)和液晶态的清亮点(T_i)呈规律性变化,近晶相范围和近晶相-向列相转变温度渐增,而向列相温度范围递减,至十二烷基时,仅呈现近晶性.     

5-{[(4′-正戊基氧-4-联苯基基)羰基]氧}-1-戊炔的相转变与相结构

采用差示扫描量热(DSC)、一维(1D)广角X射线衍射(WAXD)、热台偏光显微镜(PLM-hotstage)等研究手段对含联苯液晶基元的侧链液晶聚炔单体5-{[(4′-正戊基氧-4-联苯基基)羰基]氧}-1-戊炔(A3EO5)的本体相转变和相结构进行了研究.DSC和1D-WAXD实验结果表明,A3EO5在升温和降温过程中均呈现四个相转变过程,形成双向性液晶.样品从各向同性态降温至室温过程中,首先形成近晶A相,随后进入层内排列具有准长程有序的近晶B相,继续降温将形成层内为正交排列的近晶E相,在此之后样品进入晶相.PLM结果指出样品在各向同性态降温过程中分别形成球状织构、角锥织构和同心圆弧织构.     

双枝芳醚树枝形聚合物构象研究

合成了外围只以一个芘基团修饰、核心为苯胺的双枝芳醚树枝形聚合物Py-[Gn]2-NPh (n＝1～2), 利用分子内电子转移和激基复合物的形成对其折叠构象和折叠程度进行了研究. 二氯甲烷溶液中选择性激发芘基团, 树枝形聚合物Py-[Gn]2-NPh分子内发生从苯胺到芘基团之间的电子转移, 观察到了分子内外围芘基团和核心苯胺基团之间形成激基复合物的发光, 为芳醚树枝形聚合物折叠构象的存在给出了直接实验观察. 二氯甲烷溶液中1～2代Py-[Gn]2-NPh分子内电子转移效率分别为0.87和0.81, 速率常数分别为2.3×108和1.5×108 s－1. 利用电子转移速率常数估算得到1～2代Py-[Gn]2-NPh分子内给、受体之间的距离分别为0.79和0.81 nm, 说明双枝芳醚树枝形聚合物与单枝结构类似, 其外围基团也可以折叠到达分子内部接近核心的位置.     

非线性光学活性的侧链型聚丙二酸酯液晶的合成和性质

通过熔融缩聚法合成了含非线性光学活性硝基偶氮苯液晶基元的聚丙二酸酯侧链液晶聚合物 ,采用FTIR、NMR对其结构进行了表征 ,DSC确定其液晶转变温度 ,并用变温WAXD及偏光显微镜 (POM )研究其液晶性质 ,该聚合物为近晶型液晶聚合物 ,POM观察到典型焦锥织构 ,近晶相WAXD有对应层间距为2 74nm和 1 35nm的两个衍射峰 .聚合物旋涂膜经电晕极化 ,紫外光谱测试求得其取向序参数 =0 33 .     

Disclination and molecular director studies on bowlic columnar nematic phase using mosaic-like morphology decoration method

Two bowlic cyclotriveratrylene CTV-1 and CTV-2, with different peripheral groups of —OCH₃ and —OCH₂CH₃ for CTV-1 and —OCH₃ and —OCH₂COOCH₃ for CTV-2, respectively, were synthesized by typical trimerization via a multistep sequence from vanillin. Both bowlic CTV molecules were thermotropic liquid crystals, and presented typical grainy textures of the nematic phase and homogeneous texture of the single domain nematic phase. It is of interest to observe the regular and beautiful mosaic-like morphologies after cooling from liquid crystalline phases, which appeared and vanished repeatedly in several circles of cooling and heating. The size of each mosaic was several dozens of micron. In nature, the mosaic-like morphologies are the optical pattern of cracks formed by the shrinking, due to the crystallization of frozen texture of nematic phases. By means of scanning electron microscopy, the mosaic-like morphologies were observed to consist of lamellae, and each mosaic is a rectangular multi-layer lamella, which is composed of packed single-layered lamellae. The fibrils in the diameter of about 1 μm were observed, which are the structural units of lamellae and would be the bundles of the bowlic molecular columns. The mosaic-like morphologies decorate the bowlic molecular columnar nematic phase, therefore, a novel mosaic-like morphologies decoration method was applied to reveal the director distribution of several kinds of point disclinations, such as s = +1(δ=0° and δ =90 °) and s = ±1/2, and Nèel domain walls. It was shown that the bowlic molecular columnar nematic phase behaved as normal nematic phases; however, the basic structural units ordered were the bowlic molecular column or the bundles of bowlic molecular column (i.e. fibrils), but not the bowlic molecules themselves. The bowlic molecular columns acted as the rod-like molecules in a normal nematic phase. Therefore, a new term BCN (bowlic columnar nematic phase) is used to describe the anomalous nematic phase in this paper. Supported by the National Natural Science Foundation of China (Grant No. 20774077), the Natural Science Foundation of Fujian, China (Grant Nos. E0510003 & E0710025) and the Project of Science and Technology of Xiamen, China (Grant No. 3502Z20055013)     

Hydrogelators of cyclotriveratrylene derivatives

Developing cavity-based supramolecular hydrogels is in its infancy because not many such hydrogelators are available. Reported herein is our creation of rigid cavitand cyclotriveratrylene (CTV) based hydrogelators from the molecular backbones of CTVs that were in limited cases shown to form organogels. For doing so deprotonable -COOH or protonable -NH(2) was introduced as terminal group into the rigid and hydrophobic CTV backbones. We thus successfully obtained optically anisotropic supramolecular hydrogels from these new CTVs hydrogelators with excellent thermostability and high tolerance towards strong electrolytes. The obtained CTV-1 and CTV-2 hydrogels are luminescent and exhibit reversible gel-to-sol and sol-to-gel transitions upon pH variations. The success in creating CTV-1 and CTV-2 hydrogelators on the basis of the skeleton of a CTV-organogelator suggests that balancing the hydrophilic and hydrophobic characters of the ionic and hydrophobic moieties well in the gelator molecule is important for designing a promising hydrogelator.     

Synthesis and Crystal Structure of a 1-D Chain Coordination Complex {[Mn2(HCAM)3(H2bipy)]·5H2O}n

The 1-D chain coordination complex of {[Mn2(HCAM)3(H2bipy)]·5H2O}n(H3CAM=4-hydroxypyridine-2,6-dicarboxylic acid,bipy=4,4′-bipyridine) has been synthesized by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid,4,4′-bipyridine and manganese carbonate under hydrothermal conditions,and its crystal structure was determined by X-ray diffraction method.The crystal belongs to the monoclinic system,space group P21/n with a=10.110(2),b=20.159(4),c=17.861(4) ,β=99.67(3)°,V=3.5884(12) nm3,Mr=901.47,Z=4,Dc=1.669 g·cm-3,μ=0.798 mm-1,F(000)=1840,the final R=0.0713 and wR=0.1853.The complex forms a 1-D chain bridged by HCAM,protonated 4,4-bipyridines link the 1-D chains to construct 2-D networks via N-H…O hydrogen bonds,and networks are further extended via π-π stacking and hydrogen bonds into 3-D supramolecular framework.     

Synthesis and Crystal Structure of 3-（2,4-Dichlorophenyl）- 4-dydroxy-5-cyclohexanyl-△3-dihydrofuran-2-one

The title compound 3-（2,4-dichlorophenyl）-4-dydroxy-3-（2,4-dichlorophenyl）-4- dydroxy-5-cyclohexanyl-A3-dihydrofuran-2-one 5 has been synthesized by the cyclization of methyl O-（2,4-dichlorophenyl-acetyl）-1-hydroxycyclo-hexane-carboxylate 4, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group Pi with a = 6.8192（3）, b = 10.5053（5）, c = 10.5811（5）A,α = 71.681（10）, β = 78.905（12）, γ = 81.036（12）°, C15H14C1203, Mr = 313.18, V= 702.44（6）A3, Z = 2, De= 1.481 g/cm^3, F（000） = 324,μ = 0.465 mm^-1, S = 1.006, the final R = 0.0331 and wR = 0.1363 for 2505 observed reflections with I 〉 2σ（I） and 183 variable parameters. The crystal analysis shows that the cyclohexene unit of the title compound has a quasi-chair conformation, and a one-dimensional chain structure is formed via the intermolecular hydrogen bond O（1）-H（101）…O（2）.     

Synthesis and Structural Characterization of Pd[CH3O（O）C6H3CHNNC（S）NH2]（C5H5N）

1 INTRODUCTION Palladium (Ⅱ) coordination and organometallic compounds usually show square planar environments at the metal center[1], and have experienced an im- portant development in the past years due to their acting as intermediates in different types of catalytic reactions and numerous applications in organic synthesis[2]. Although palladium plays an increase- ingly recognized role as a biometal[3], little is known about the structure and function of palladium compounds in living …     

Synthesis and Crystal Structure of Chiral Spiro{1-bromo-4-hydroxy-5-N-cyclohexyl-butyrolactam-6-oxo-dirings[3.1.0]hexane-2,3′-(4′-diphenylcarbinol-5′-menthyloxy-butyrolatone)}

A novel compound of chiral spiro{1-bromo-4-hydroxy-5-N-cyclohexyl-butyro-lactam-6-oxo-dirings3.1.0hexane-2,3′-(4′-diphenylcarbinol-5′-menthyloxy-butyrolatone)} was synthesized via tandem nucleophilic substitution reaction under mild conditions=and its structure was determined by IR =1H NMR=elemental analysis and X-ray diffraction.The crystal structure of this compound is of monoclinic system=space group P21 with a=9.7356(9)=b=12.2760(12)=c=14.9577(14)=β=101.0300(10)°=Mr=680.66=Z=2=V=1754.6(3)3=Dc=1.288 g/cm3=μ(MoKα)=1.216 mm-1=F(000)=716=the final R=0.0434 and wR=0.0996.     

Synthesis and Crystal Structure of Chiral Spiro{1-bromo-4-hydroxy-5-N-cyclohexyl- butyrolactam-6-oxo-dirings[3.1.0]hexane-2,3?-(4?-diphenylcarbinol-5?-menthyloxy-butyrolatone)}

A novel compound of chiral spiro{1-bromo-4-hydroxy-5-N-cyclohexyl-butyro- lactam-6-oxo-dirings[3.1.0]hexane-2,3?-(4?-diphenylcarbinol-5?-menthyloxy-butyrolatone)} was synthesized via tandem nucleophilic substitution reaction under mild conditions, and its structure was determined by IR , 1H NMR, elemental analysis and X-ray diffraction. The crystal structure of this compound is of monoclinic system, space group P21 with a = 9.7356(9), b = 12.2760(12), c = 14.9577(14) ?, β = 101.0300(10)°, Mr = 680.66, Z = 2, V = 1754.6(3) ?3, Dc = 1.288 g/cm3, μ(MoKα) = 1.216 mm-1, F(000) = 716, the final R = 0.0434 and wR = 0.0996.     

一水合(E)-N'-(5-氯-2-羟基苯亚甲基)-2-(8-羟基喹啉基)-乙酰肼Schiff碱的合成及其晶体结构

在甲醇溶液中,5-氯水杨醛和8-羟基喹啉乙酰肼经缩合反应合成了新化合物--一水合(E)-N'-(5-氯-2-羟基苯亚甲基)-2-(8-羟基喹啉基)-乙酰肼Schiff碱(1),其结构经1H NMR,IR,元素分析和X-射线单晶衍射表征.1属正交晶系,P2_12_12_1空间群,晶胞参数:a=4.748(5) (A),b=15.818(14) (A),c=22.802(2) (A),α=β=γ=90.00 °,V=1 712.0(3) (A)~3,Z=4,Dc=1.450 g·cm~(-3),μ=0.253 mm~(-1),F(000) =776,R_1=0.072 5,wR_2=0.102.1通过氢键相互作用,连接成一维无限链结构.     

Synthesis, Crystal Structure and Band Structure of Sm3In5

A new intermetallic compound, Sm3In5, has been synthesized by solid-state reaction of the corresponding pure elements in a welded niobium tube at high temperature. Its crystal structure was established by single-crystal X-ray diffraction. Sm3In5 crystallizes in orthorhombic, space group Cmcm with a = 10.0137(8), b = 8.1211(7), c = 10.3858(8) , V = 844.60(1) 3, Z = 4, Mr = 1025.15, Dc = 8.062 g/cm3, μ = 33.791 mm-1, F(000) = 1724, the final R = 0.0346 and wR = 0.0775 for 533 observed reflections with I > 2σ(I). The structure of Sm3In5 belongs to the modified Pu3Pd5 type. It is isostructural with La3In5 and β-Y3In5, containing one-dimensional (1D) [In5] cluster chains along the c-axis, which are weakly interconnected via In-In bonds (3.345 ) to form a three-dimensional (3D) structure. The samarium cations are located at the voids between the 1D [In5] cluster chains. Band structure calculations based on Density Function Theory (DFT) method indicate that Sm3In5 is metallic.     

新型手性希夫碱镍配位聚合物的合成及其晶体结构

以手性对称的Schiff碱为配体,合成了手性镍配合物[Ni2(salen)2(1)],其结构经X-单晶射线衍射和元素分析表征。1属单斜晶系,C2空间群,晶胞参数a=25.060(5)A,b=13.508(3),c=11.938(2),α=90(3)°,β=104.82(3)°,γ=90(3)°,V=3 906.7(14)3,Z=4,Mr=828.24,Dc=1.429 g.cm-3,F(000)=1 808,μ=1.027 mm-1,GOF=1.068,R1=0.051 0,wR2=0.128 9。在1的分子结构中,环己胺和苯环之间通过分子间CH┈π作用形成二维结构。